WO2011136189A1 - Solution d'électrolyte non aqueuse contenant un composé sulfone cyclique, et batterie secondaire au lithium - Google Patents

Solution d'électrolyte non aqueuse contenant un composé sulfone cyclique, et batterie secondaire au lithium Download PDF

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WO2011136189A1
WO2011136189A1 PCT/JP2011/060093 JP2011060093W WO2011136189A1 WO 2011136189 A1 WO2011136189 A1 WO 2011136189A1 JP 2011060093 W JP2011060093 W JP 2011060093W WO 2011136189 A1 WO2011136189 A1 WO 2011136189A1
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carbon atoms
general formula
substituted
hydrogen atom
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PCT/JP2011/060093
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Japanese (ja)
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三尾　茂
中村　光雄
野木　栄信
林　剛史
剛史 小林
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三井化学株式会社
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Priority to EP11774970.5A priority Critical patent/EP2565973B1/fr
Priority to CN201180020472.8A priority patent/CN102870268B/zh
Priority to JP2012512837A priority patent/JP5399556B2/ja
Priority to US13/643,302 priority patent/US9303011B2/en
Priority to KR1020127029926A priority patent/KR101422383B1/ko
Publication of WO2011136189A1 publication Critical patent/WO2011136189A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/035—Liquid electrolytes, e.g. impregnating materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/64—Liquid electrolytes characterised by additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a non-aqueous electrolyte excellent in output characteristics, a lithium secondary battery using the same, and a lithium secondary battery additive useful as an additive for the electrolyte.
  • the lithium secondary battery is mainly composed of a positive electrode and a negative electrode containing a material capable of occluding and releasing lithium, and a non-aqueous electrolyte containing a lithium salt and a non-aqueous solvent.
  • the positive electrode active material used for the positive electrode for example, lithium metal oxides such as LiCoO 2 , LiMnO 2 , LiNiO 2 , and LiFePO 4 are used.
  • Nonaqueous electrolytes include mixed solvents (nonaqueous solvents) of carbonates such as ethylene carbonate, propylene carbonate, ethylene carbonate, and methyl carbonate, LiPF 6 , LiBF 4 , LiN (SO 2 CF 3 ) 2 and LiN ( A solution in which a Li electrolyte such as SO 2 CF 2 CF 3 ) 2 is mixed is used.
  • carbonates such as ethylene carbonate, propylene carbonate, ethylene carbonate, and methyl carbonate
  • LiPF 6 LiBF 4
  • LiN (SO 2 CF 3 ) 2 and LiN A solution in which a Li electrolyte such as SO 2 CF 2 CF 3 ) 2 is mixed is used.
  • active materials for negative electrodes used for negative electrodes metal lithium, metal compounds capable of occluding and releasing lithium (metal simple substance, oxide, alloy with lithium, etc.) and carbon materials are known.
  • the present invention has been made to meet the above-mentioned problems, and an object of the present invention is to provide a non-aqueous electrolytic solution that improves battery output characteristics by keeping the resistance value of the battery low, and the non-aqueous electrolytic solution. And providing a lithium secondary battery with improved resistance.
  • a further object of the present invention is to provide an additive for a lithium secondary battery useful for such a non-aqueous electrolyte.
  • the present inventor has suppressed the increase in resistance of the battery by adding a specific additive to the non-aqueous electrolyte of the lithium secondary battery.
  • a new additive a novel compound was found and the present invention was completed. That is, the present invention is as follows.
  • a nonaqueous electrolytic solution containing a compound having a 1,3-dithietane-1,1,3,3-tetraoxide skeleton ⁇ 2> The nonaqueous electrolysis according to ⁇ 1>, wherein the compound having a 1,3-dithietane-1,1,3,3-tetraoxide skeleton is a cyclic sulfone compound represented by the following general formula (I): liquid.
  • R 1 , R 2 , R 3 and R 4 are each independently Hydrogen atom, Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, A substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, A substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, -SiR 7 R 8 R 9 group (R 7 , R 8 and R 9 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a phenyl group), -CO 2 R 10 group (R 10 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or the aforementioned -SiR 7 R 8 R 9 group), -COR 11 group (R 11 represents a substituted or unsubstituted
  • R 1 and R 2 may be bonded to each other to form a cycloalkane group having 3 to 7 carbon atoms together with the carbon atom to which R 1 and R 2 are bonded.
  • a methylene group represented by (II) (in the general formula (II), R 5 and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a group having 2 to 12 carbon atoms); Represents a dialkylamino group, R 5 and R 6 may be bonded to each other to form a cycloalkane group having 3 to 7 carbon atoms together with the carbon atom to which R 5 and R 6 are bonded. May be.
  • R 3 and R 4 may be bonded to each other to form a cycloalkane group having 3 to 7 carbon atoms together with the carbon atom to which R 3 and R 4 are bonded.
  • a methylene group represented by (II) (in the general formula (II), R 5 and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a group having 2 to 12 carbon atoms); Represents a dialkylamino group, and R 5 and R 6 may combine with each other to form a C 3-7 cycloalkane group together with a carbon atom. ]
  • R 1 and R 2 are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 6 carbon atoms, Or —SiR 7 R 8 R 9 group (R 7 , R 8 and R 9 are each independently an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group).
  • R 1 and the R 2 are bonded to each other to form a cycloalkane group having 3 to 6 carbon atoms together with the carbon atom to which the R 1 and the R 2 are bonded, or the R 1 and the R 2 Together methylene group represented by the general formula (II) (in the general formula (II), R 5 and R 6 each independently represents a hydrogen atom or a dialkylamino group having 2 to 12 carbon atoms) .) R 3 and R 4 are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 6 carbon atoms, or —SiR 7 R 8 R 9 group (R 7 , R 8 and R 9 are each independently an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group), or , The
  • R 1 and R 2 are each independently a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an allyl group, a trimethylsilyl group, or dimethyl t-butylsilyl.
  • R 1 and the R 2 are bonded to each other to form a cyclopentyl group together with the carbon atom to which the R 1 and the R 2 are bonded, or the R 1 and the R 2 are combined to form the general Forming a methylene group represented by the formula (II) (in the general formula (II), one of R 5 and R 6 is a hydrogen atom, and the other of R 5 and R 6 is a dimethylamino group);
  • R 3 and R 4 are each independently a hydrogen atom, fluorine atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, allyl group, trimethylsilyl group, dimethyl t-butylsilyl group, triethyl A silyl group or a triisopropylsilyl group, or The R 3 and
  • Y 1 and Y 2 each independently represent a hydrogen atom, a methyl group, an ethyl group, or a propyl group.
  • X 1 , X 2 , X 3 and X 4 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl having 1 to 3 carbon atoms which may be substituted with a fluorine atom. Indicates a group. However, X 1 , X 2 , X 3 and X 4 are not simultaneously hydrogen atoms. ]
  • R 1 , R 2 , R 3 and R 4 are each independently Hydrogen atom, Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, A substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, A substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, -SiR 7 R 8 R 9 group (R 7 , R 8 and R 9 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a phenyl group), -CO 2 R 10 group (R 10 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or the aforementioned -SiR 7 R 8 R 9 group), -COR 11 group (R 11 represents a substituted or unsubstituted
  • R 1 and R 2 may be bonded to each other to form a cycloalkane group having 3 to 7 carbon atoms together with the carbon atom to which R 1 and R 2 are bonded.
  • a methylene group represented by (II) (in the general formula (II), R 5 and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a group having 2 to 12 carbon atoms); Represents a dialkylamino group, R 5 and R 6 may be bonded to each other to form a cycloalkane group having 3 to 7 carbon atoms together with the carbon atom to which R 5 and R 6 are bonded. May be.
  • R 3 and R 4 may be bonded to each other to form a cycloalkane group having 3 to 7 carbon atoms together with the carbon atom to which R 3 and R 4 are bonded.
  • a methylene group represented by (II) (in the general formula (II), R 5 and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a group having 2 to 12 carbon atoms); Represents a dialkylamino group, and R 5 and R 6 may combine with each other to form a C 3-7 cycloalkane group together with a carbon atom. ]
  • the resistance value of the battery can be reduced, and the resistance value using the non-aqueous electrolyte can be increased.
  • An improved high-power lithium secondary battery can be provided.
  • the additive for lithium secondary batteries useful for such a non-aqueous electrolyte can be provided.
  • the cyclic sulfone compound according to the present invention a nonaqueous electrolytic solution using the cyclic sulfone compound, and a lithium secondary battery using the nonaqueous electrolytic solution will be specifically described.
  • the nonaqueous electrolytic solution of the present invention contains a cyclic sulfone compound having a 1,3-dithietane-1,1,3,3-tetraoxide skeleton (hereinafter also referred to as “specific cyclic sulfone compound”).
  • specific cyclic sulfone compound a cyclic sulfone compound represented by the following general formula (I) (hereinafter also referred to as “compound represented by general formula (I)”) is preferable.
  • R 1 , R 2 , R 3 and R 4 are each independently Hydrogen atom, Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, A substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, A substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, -SiR 7 R 8 R 9 group (R 7 , R 8 and R 9 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a phenyl group), -CO 2 R 10 group (R 10 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or the aforementioned -SiR 7 R 8 R 9 group), -COR 11 group (R 11 represents a substituted or unsubstituted
  • R 1 and R 2 may be bonded to each other to form a C 3-7 cycloalkane group together with the carbon atom to which R 1 and R 2 are bonded.
  • R 1 and R 2 together represent a methylene group represented by the above general formula (II) (in general formula (II),
  • R 5 and R 6 are each independently a hydrogen atom, carbon number 1 alkyl group of 1-10, a phenyl group or .
  • R 5 and R 6 represents a dialkylamino group having a carbon number of 2 to 12, 3 carbon together with the carbon atoms to which are bonded the R 5 and the R 6 bind to each other, To 7 cycloalkane groups may be formed).
  • R 3 and R 4 may be bonded to each other to form a cycloalkane group having 3 to 7 carbon atoms together with the carbon atom to which R 3 and R 4 are bonded.
  • R 3 and R 4 together represent a methylene group represented by the general formula (II) (in the general formula (II), R 5 and R 6 are each independently a hydrogen atom, carbon number 1 Represents an alkyl group of ⁇ 10, a phenyl group, or a dialkylamino group having 2 to 12 carbon atoms, and R 5 and R 6 may be bonded to each other to form a cycloalkane group of 3 to 7 carbon atoms with carbon atoms. .) May be formed.
  • alkyl group having 1 to 10 carbon atoms means methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, 2-methylbutyl, 1-methylpentyl. Specific examples thereof include neopentyl, 1-ethylpropyl, hexyl, 3,3-dimethylbutyl, heptyl, octyl, nonyl and decyl.
  • the alkyl group preferably has 1 to 6 carbon atoms.
  • the “alkenyl group having 2 to 10 carbon atoms” means vinyl, allyl, butenyl, buten-3-yl, pentenyl, penten-4-yl, hexenyl, hexen-5-yl, heptenyl Specific examples include octenyl, nonenyl, and decenyl.
  • the alkenyl group preferably has 2 to 6 carbon atoms.
  • the “alkynyl group having 2 to 10 carbon atoms” refers to ethynyl, propargyl, butyn-4-yl, butyn-3-yl, pentynyl, pentyn-4-yl, hexyn-5-yl Specific examples include heptin-7-yl, octin-8-yl, nonin-9-yl and decin-10-yl.
  • the alkynyl group preferably has 2 to 6 carbon atoms.
  • dialkylamino group having 2 to 12 carbon atoms refers to an amino acid having a linear or branched alkyl group having 2 to 12 carbon atoms.
  • specific examples are dimethylamino, diethylamino, dipropylamino, dibutylamino, dipentylamino, dihexylamino, diisopropylamino, diisobutylamino, methylethylamino, methylpropylamino, methylbutylamino, methylpentylamino, methylhexylamino As mentioned.
  • —SiR 17 R 18 R 19 groups and trimethylsilyl, triethylsilyl, triisopropylsilyl, dimethyl-t-butylsilyl, dimethylvinylsilyl, dimethylallylsilyl, dimethylphenylsilyl, diphenylmethylsilyl, triphenylsilyl, etc.), hydroxyl, cyano, acetyl , Propionyl, benzoyl, carboxyl, methoxycarbonyl, ethoxy Rubonyl, trimethylsilyloxycarbonyl, trimethylsilylmethoxycarbonyl, 2-trimethylsilylethoxycarbonyl, phenyl, pyridyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl, trifluoromethylsulfonyl, difluorophenylsulfonyl, phenylsulfonyl,
  • the substituent in the “substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms” includes 1 to 10 fluorine atoms, and 1 to 2 —SiR 17 R 18 R 19, respectively.
  • Groups (R 17 , R 18 and R 19 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a phenyl group.
  • —SiR 17 R 18 R 19 groups and trimethylsilyl, triethylsilyl, triisopropylsilyl, dimethyl-t-butylsilyl, dimethylvinylsilyl, dimethylallylsilyl, dimethylphenylsilyl, diphenylmethylsilyl, triphenylsilyl, etc.), hydroxyl, cyano, acetyl , Propionyl, benzoyl, carboxyl, methoxycarbonyl, ethoxy Carbonyl, trimethylsilyloxycarbonyl, trimethylsilylmethoxycarbonyl, 2-trimethylsilylethoxycarbonyl, phenyl, pyridyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl, trifluoromethylsulfonyl, difluorophenylsulfonyl, phenylsulfonyl
  • R 17 , R 18 and R 19 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a phenyl group.
  • —SiR 17 R 18 R 19 groups and trimethylsilyl, triethylsilyl, triisopropylsilyl, dimethyl-t-butylsilyl, dimethylvinylsilyl, dimethylallylsilyl, dimethylphenylsilyl, diphenylmethylsilyl, triphenylsilyl, etc.), hydroxyl, cyano, acetyl , Propionyl, benzoyl, carboxyl, methoxycarbonyl, ethoxy Carbonyl, trimethylsilyloxycarbonyl, trimethylsilylmethoxycarbonyl, 2-trimethylsilylethoxycarbonyl, phenyl, pyridyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl, trifluoromethylsulfonyl, difluorophenylsulfonyl, phenylsulfonyl
  • R 1 and R 2 are bonded to each other, and may be formed together with the carbon atom to which R 1 and R 2 are bonded. , Cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and the like.
  • R 3 and R 4 may be bonded to each other, and may be formed together with the carbon atom to which R 3 and R 4 are bonded. , Cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and the like.
  • R 5 and R 6 are bonded to each other, and may be formed together with the carbon atom to which R 5 and R 6 are bonded.
  • Examples of the “cycloalkane group of 3 to 7” include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and the like.
  • —SiR 7 R 8 R 9 group (R 7 , R 8 and R 9 are each independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or phenyl”
  • Examples of “representing a group” include trimethylsilyl, triethylsilyl, triisopropylsilyl, dimethyl-t-butylsilyl, dimethylvinylsilyl, dimethylallylsilyl, dimethylphenylsilyl, diphenylmethylsilyl, triphenylsilyl and the like.
  • —CO 2 R 10 group (where R 10 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or the —SiR 7 R 8 R 9 group,
  • R 10 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or the —SiR 7 R 8 R 9 group
  • carboxy methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, isobutoxycarbonyl, t -Butoxycarbonyl, trimethylsilyloxycarbonyl, trimethylsilylmethyloxycarbonyl, 2-trimethylsilylethyl
  • —COR 11 group (R 11 represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group)” includes acetyl, propionyl, butyryl, pentanoyl, hexanoyl, Examples include heptanoyl, octanoyl, nonanoyl, decanoyl, isobutyryl, pivaloyl, benzoyl, trifluoroacetyl, and the like.
  • —P (O) (OR 12 ) 2 group R 12 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or the —SiR 7 R 8 R 9 represents a group) ”includes phosphono, dimethoxyphosphono, diethoxyphosphono, dipropoxyphosphono, dibutoxyphosphono, dipentoxyphosphono, dihexyloxyphosphono, diheptyloxyphosphono, Dioctyloxyphosphono, dinonyloxyphosphono, didecyloxyphosphono, diisobutoxyphosphono, bis (trimethylsilyloxy) phosphono, bis (trimethylsilylmethyloxy) phosphono, bis (2-trimethylsilylethyloxy) phosphono, 2,2 , 2-trifluoroethyloxyphosphono, 2-cyanoethy
  • —SO 2 R 13 group (R 13 represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a phenyl group)” is methylsulfonyl, ethylsulfonyl, Examples include propylsulfonyl, butylsulfonyl, pentylsulfonyl, hexylsulfonyl, heptylsulfonyl, octylsulfonyl, nonylsulfonyl, decylsulfonyl, isobutylsulfonyl, t-butylsulfonyl, phenylsulfonyl, trifluoromethylsulfonyl, and the like.
  • a “—SO 2 (OR 14 ) group (R 14 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or the —SiR 7 R 8 R 9,” Represents methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, butoxysulfonyl, pentoxysulfonyl, hexyloxysulfonyl, heptyloxysulfonyl, octyloxysulfonyl, nonyloxysulfonyl, decyloxysulfonyl, isobutoxysulfonyl, t -Butoxysulfonyl, trimethylsilyloxysulfonyl, trimethylsilylmethyloxysulfonyl, 2-trimethylsilylethyloxysulfony
  • R 15 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or the aforementioned —SiR 7 R 8 R 9.
  • R 1 and R 2 are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 6 carbon atoms, or —SiR 7 R 8 R 9 group (R 7 , R 8 and R 9 are each independently an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group), or ,
  • the R 1 and the R 2 are bonded to each other to form a cycloalkane group having 3 to 6 carbon atoms together with the carbon atom to which the R 1 and the R 2 are bonded, or the R 1 and the R 2 Together methylene group represented by the general formula (II) (in the general formula (II), R 5 and R 6 each independently represents a hydrogen atom or a dialkylamino group having 2
  • R 1 and R 2 are each independently a hydrogen atom, fluorine atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, allyl group, trimethylsilyl group, dimethyl t-butylsilyl group, triethyl A silyl group or a triisopropylsilyl group, or
  • the R 1 and the R 2 are bonded to each other to form a cyclopentyl group together with the carbon atom to which the R 1 and the R 2 are bonded, or the R 1 and the R 2 are combined to form the general Forming a methylene group represented by the formula (II) (in the general formula (II), one of R 5 and R 6 is a hydrogen atom, and the other of R 5 and R 6 is a dimethylamino group);
  • R 3 and R 4 are each independently a hydrogen atom, fluorine atom, methyl group, ethyl group
  • R 1 and R 2 are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms), a substituted or unsubstituted carbon number.
  • R 7 , R 8 and R 9 each independently represents 1 to 10 carbon atoms (more preferably An alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 10 carbon atoms (more preferably an alkenyl group having 2 to 6 carbon atoms, or a phenyl group), or bonded to each other and the R 1 and the R Forming a cycloalkane group having 3 to 7 carbon atoms (more preferably 3 to 6 carbon atoms) together with the carbon atom to which 2 is bonded;
  • R 3 and R 4 are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms), a substituted or unsubstituted carbon number.
  • R 7 , R 8 and R 9 each independently represents 1 to 10 carbon atoms (more preferably An alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 10 carbon atoms (more preferably an alkenyl group having 2 to 6 carbon atoms, or a phenyl group), or bonded to each other and the R 3 and the R
  • a cycloalkane group having 3 to 7 carbon atoms is formed together with the carbon atom to which 4 is bonded.
  • R 1 and R 2 are each independently a hydrogen atom, fluorine atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, trimethylsilyl group, dimethyl t-butylsilyl group, triethylsilyl group, Or a triisopropylsilyl group, or bonded to each other to form a cyclopentyl group together with the carbon atom to which R 1 and R 2 are bonded;
  • R 3 and R 4 are each independently a hydrogen atom, fluorine atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, trimethylsilyl group, dimethyl t-butylsilyl group, triethylsilyl group, Or it is a triisopropylsilyl group, or it is a form which couple
  • the compound represented by the general formula (I) is preferably a compound other than the compound in which R 1 , R 2 , R 3 and R 4 in the general formula (I) are all hydrogen atoms.
  • the form of the cyclic sulfone compound represented by the following general formula (A) or the following general formula (B) is also exemplified.
  • R 17 , R 18 , and R 19 each independently represent an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a phenyl group.
  • Two R 17 s , R 18 s , and R 19 s each present in the general formula (A) may be the same or different.
  • Ra and Rb each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a phenyl group.
  • Me represents a methyl group
  • Et represents an ethyl group
  • Pr represents a propyl group
  • iPr represents an isopropyl group
  • Bu represents a butyl group
  • sBu Is a secondary butyl group
  • iBu is an isobutyl group
  • tBu is a tertiary butyl group
  • Pent is a pentyl group
  • Hex is a hexyl group
  • Hept is a heptyl group
  • Oct is a pentyl group
  • the cyclic sulfone compound represented by the general formula (I) of the present invention can be produced by a method described in the following known literature, but is not limited to this production method. Chemishche Berichte, 1981, 114, 3378-3384. Chemishche Berichte, 1991, 124, 1805-1807. Chemishche Berichte, 1993, 126, 537-542. Chemishche Berichte, 1993, 126, 537-542. Chemishche Berichte, 1996, 129, 161-168. Angewandte Chemie, 1980, 92, 223-224 Russian Journal of Organic Chemistry, 1993, 29, 479-481. Russian Journal of Organic Chemistry, 1995, 31, 543-544. Russian Journal of Organic Chemistry, 1995, 31, 543-544. Phosphorous, Slufur and Silicon and Related Elements, 1994, 94, 477-478. Journal of American Chemical Society, 1996, 108, 2358-2366. SU 311908 (1971)
  • the cyclic sulfone compound represented by the general formula (I) is useful as an additive for a lithium secondary battery, particularly as an additive for a non-aqueous electrolyte solution of a lithium secondary battery described later.
  • the additive for lithium secondary batteries of the present invention is an additive for lithium secondary batteries containing the compound represented by the general formula (I) as an active ingredient.
  • the additive for a lithium secondary battery of the present invention may contain only one compound represented by the general formula (I) or two or more compounds represented by the general formula (I). You may go out.
  • the additive for lithium secondary batteries of this invention may contain the other component in addition to the compound represented by general formula (I) as needed.
  • the other component from the viewpoint of obtaining the above effect more effectively, for example, at least one compound represented by the following general formula (III) or the following general formula (IV) (more preferably, the general At least one of the compounds represented by formula (III) can be used.
  • the nonaqueous electrolytic solution of the present invention is characterized by containing the specific cyclic sulfone compound, but the other components can optionally include known ones.
  • the specific cyclic sulfone compound contained in the nonaqueous electrolytic solution of the present invention may be only one type or two or more types may be used in combination.
  • the content of the specific cyclic sulfone compound in the nonaqueous electrolytic solution of the present invention is preferably 0.001% by mass to 10% by mass, and more preferably 0.05% by mass to 5% by mass. preferable. In this range, it is possible to suppress an increase in resistance of the battery with time and achieve high output.
  • the nonaqueous electrolytic solution generally contains an electrolyte and a nonaqueous solvent.
  • Nonaqueous solvent As the non-aqueous solvent in the present invention, various known ones can be appropriately selected, but it is preferable to use a cyclic aprotic solvent and / or a chain aprotic solvent. In order to improve the safety of the battery, when aiming to improve the flash point of the solvent, it is preferable to use a cyclic aprotic solvent as the non-aqueous solvent.
  • Cyclic aprotic solvent As the cyclic aprotic solvent, cyclic carbonate, cyclic carboxylic acid ester, cyclic sulfone, and cyclic ether can be used.
  • the cyclic aprotic solvent may be used alone or in combination of two or more.
  • the mixing ratio of the cyclic aprotic solvent in the non-aqueous solvent is 10% by mass to 100% by mass, more preferably 20% by mass to 90% by mass, and particularly preferably 30% by mass to 80% by mass. By setting it as such a ratio, the electroconductivity related to the charge / discharge characteristics of the battery can be increased.
  • cyclic carbonate examples include ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, and the like.
  • ethylene carbonate and propylene carbonate having a high dielectric constant are preferably used.
  • ethylene carbonate is more preferable.
  • cyclic carboxylic acid esters include ⁇ -butyrolactone, ⁇ -valerolactone, or alkyl-substituted products such as methyl ⁇ -butyrolactone, ethyl ⁇ -butyrolactone, and ethyl ⁇ -valerolactone.
  • the cyclic carboxylic acid ester has a low vapor pressure, a low viscosity, a high dielectric constant, and can lower the viscosity of the electrolytic solution without lowering the degree of dissociation between the flash point of the electrolytic solution and the electrolyte.
  • a cyclic carboxylic acid ester as the cyclic aprotic solvent.
  • a cyclic carboxylic acid ester is preferably used by mixing with another cyclic aprotic solvent. Examples thereof include a mixture of a cyclic carboxylic acid ester and a cyclic carbonate and / or a chain carbonate.
  • cyclic carboxylic acid esters and cyclic carbonates and / or chain carbonates include ⁇ -butyrolactone and ethylene carbonate, ⁇ -butyrolactone and ethylene carbonate and dimethyl carbonate, and ⁇ -butyrolactone and ethylene carbonate and methylethyl.
  • ⁇ -butyrolactone ethylene carbonate, dimethyl carbonate, diethyl carbonate, ⁇ -butyrolactone, ethylene carbonate, methyl ethyl carbonate, diethyl carbonate, ⁇ -butyrolactone, ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ⁇ -butyrolactone, ethylene Carbonate and Lopylene carbonate, dimethyl carbonate and methyl ethyl carbonate, ⁇ -butyrolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate and diethyl carbonate, ⁇ -butyrolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate and diethyl carbonate, ⁇ -butyrolactone, ethylene carbonate, propylene carbonate, methyl ethyl carbonate and diethyl carbonate, ⁇ -butyrolactone and ethylene carbonate Propylene carbonate, dimethyl carbonate,
  • cyclic sulfone examples include sulfolane, 2-methyl sulfolane, 3-methyl sulfolane, dimethyl sulfone, diethyl sulfone, dipropyl sulfone, methyl ethyl sulfone, methyl propyl sulfone and the like.
  • An example of a cyclic ether is dioxolane.
  • Chain aprotic solvent a chain carbonate, a chain carboxylic acid ester, a chain ether, a chain phosphate, or the like can be used.
  • the mixing ratio of the chain aprotic solvent in the non-aqueous solvent is 10% by mass to 100% by mass, more preferably 20% by mass to 90% by mass, and particularly preferably 30% by mass to 80% by mass.
  • chain carbonate examples include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate, dipropyl carbonate, methyl butyl carbonate, ethyl butyl carbonate, dibutyl carbonate, methyl pentyl carbonate, Examples include ethyl pentyl carbonate, dipentyl carbonate, methyl heptyl carbonate, ethyl heptyl carbonate, diheptyl carbonate, methyl hexyl carbonate, ethyl hexyl carbonate, dihexyl carbonate, methyl octyl carbonate, ethyl octyl carbonate, dioctyl carbonate, and methyltrifluoroethyl carbonate.
  • These chain carbonates may be used as a mixture of two or more.
  • chain carboxylic acid ester examples include methyl pivalate.
  • chain ether examples include dimethoxyethane.
  • chain phosphate ester examples include trimethyl phosphate.
  • the non-aqueous solvent used in the non-aqueous electrolyte solution according to the present invention may be used alone or in combination. Further, only one or a plurality of cyclic aprotic solvents may be used, or only one or a plurality of chain aprotic solvents may be used, or a cyclic aprotic solvent and a chain aprotic solvent. A mixed solvent may be used. When the load characteristics and low temperature characteristics of the battery are particularly intended to be improved, it is preferable to use a combination of a cyclic aprotic solvent and a chain aprotic solvent as the nonaqueous solvent.
  • the conductivity of the electrolyte solution related to the charge / discharge characteristics of the battery can be increased by a combination of the cyclic carboxylic acid ester and the cyclic carbonate and / or the chain carbonate.
  • cyclic carbonate and chain carbonate specifically, ethylene carbonate and dimethyl carbonate, ethylene carbonate and methyl ethyl carbonate, ethylene carbonate and diethyl carbonate, propylene carbonate and dimethyl carbonate, propylene carbonate and methyl ethyl carbonate, propylene carbonate and Diethyl carbonate, ethylene carbonate and propylene carbonate and methyl ethyl carbonate, ethylene carbonate and propylene carbonate and diethyl carbonate, ethylene carbonate and dimethyl carbonate and methyl ethyl carbonate, ethylene carbonate and dimethyl carbonate and diethyl carbonate, ethylene carbonate and methyl ethyl carbonate Diethyl carbonate, ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate, ethylene carbonate and methyl ethyl carbonate Diethyl carbonate, ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate and die
  • the mixing ratio of the cyclic carbonate and the chain carbonate is expressed by mass ratio, and the cyclic carbonate: chain carbonate is 5:95 to 80:20, more preferably 10:90 to 70:30, and particularly preferably 15:85. ⁇ 55: 45.
  • the cyclic carbonate: chain carbonate is 5:95 to 80:20, more preferably 10:90 to 70:30, and particularly preferably 15:85. ⁇ 55: 45.
  • the nonaqueous electrolytic solution according to the present invention may contain a solvent other than the above as a nonaqueous solvent.
  • a solvent other than the above as a nonaqueous solvent include amides such as dimethylformamide, chain carbamates such as methyl-N, N-dimethylcarbamate, cyclic amides such as N-methylpyrrolidone, N, N-dimethylimidazolidinone, and the like.
  • examples thereof include boron compounds such as cyclic urea, trimethyl borate, triethyl borate, tributyl borate, trioctyl borate, trimethylsilyl borate, and polyethylene glycol derivatives represented by the following general formula.
  • the nonaqueous electrolytic solution of the present invention preferably contains a compound represented by the general formula (III) from the viewpoint of forming a negative electrode surface film.
  • Y 1 and Y 2 each independently represent a hydrogen atom, a methyl group, an ethyl group, or a propyl group.
  • Examples of the compound represented by the general formula (III) include vinylene carbonate, methyl vinylene carbonate, ethyl vinylene carbonate, propyl vinylene carbonate, dimethyl vinylene carbonate, diethyl vinylene carbonate, and dipropyl vinylene carbonate. Of these, vinylene carbonate is most preferred.
  • the content of the compound represented by the general formula (III) in the non-aqueous electrolyte of the present invention is although it can be appropriately selected depending on the condition, it is preferably 0.001% by mass to 10% by mass, and more preferably 0.05% by mass to 5% by mass.
  • the nonaqueous electrolytic solution of the present invention preferably contains a compound represented by the general formula (IV) from the viewpoint of forming a surface film of the negative electrode.
  • X 1 , X 2 , X 3 and X 4 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl having 1 to 3 carbon atoms which may be substituted with a fluorine atom Indicates a group. However, X 1 to X 4 are not simultaneously hydrogen atoms.
  • examples of the alkyl group having 1 to 3 carbon atoms which may be substituted by a fluorine atom of X 1 to X 4 include, for example, fluoromethyl, difluoromethyl, trifluoromethyl, pentafluoroethyl, heptafluoro And propyl.
  • known compounds can be used, for example, 4-fluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4,5-difluoroethylene carbonate, 4,4,5-trimethyl.
  • fluoroethylene carbonate and 4,4,5,5-tetrafluoroethylene carbonate are most desirable.
  • the content of the compound represented by the general formula (IV) in the nonaqueous electrolytic solution of the present invention is although it can be appropriately selected depending on the condition, it is preferably 0.001% by mass to 10% by mass, and more preferably 0.05% by mass to 5% by mass.
  • electrolytes can be used for the nonaqueous electrolytic solution of the present invention, and any of them can be used as long as it is normally used as an electrolyte for a nonaqueous electrolytic solution.
  • These electrolytes may be used alone or in combination of two or more. Of these, lithium salts are particularly desirable.
  • the electrolyte in the present invention is usually preferably contained in the nonaqueous electrolyte at a concentration of 0.1 mol / liter to 3 mol / liter, preferably 0.5 mol / liter to 2 mol / liter.
  • the nonaqueous electrolytic solution of the present invention when a cyclic carboxylic acid ester such as ⁇ -butyrolactone is used in combination as the nonaqueous solvent, it is particularly desirable to contain LiPF 6 . Since LiPF 6 has a high degree of dissociation, the conductivity of the electrolytic solution can be increased, and the reductive decomposition reaction of the electrolytic solution on the negative electrode can be suppressed. LiPF 6 may be used alone, or LiPF 6 and other electrolytes may be used. Any other electrolyte can be used as long as it is normally used as an electrolyte for a non-aqueous electrolyte, but lithium salts other than LiPF 6 are preferred among the specific examples of the lithium salts described above. .
  • the ratio of LiPF 6 in the lithium salt is 1% by mass to 100% by mass, preferably 10% by mass to 100% by mass, and more preferably 50% by mass to 100% by mass.
  • Such an electrolyte is preferably contained in the non-aqueous electrolyte at a concentration of 0.1 mol / liter to 3 mol / liter, preferably 0.5 mol / liter to 2 mol / liter.
  • the non-aqueous electrolyte of the present invention is not only suitable as a non-aqueous electrolyte for a lithium secondary battery, but also a non-aqueous electrolyte for a primary battery, a non-aqueous electrolyte for an electrochemical capacitor, and an electric double layer capacitor. It can also be used as an electrolytic solution for aluminum electrolytic capacitors.
  • the lithium secondary battery of the present invention basically comprises a negative electrode, a positive electrode, and the non-aqueous electrolyte of the present invention, and a separator is usually provided between the negative electrode and the positive electrode. .
  • metal lithium As the negative electrode active material constituting the negative electrode in the present invention, metal lithium, a lithium-containing alloy, a metal or alloy that can be alloyed with lithium, an oxide that can be doped / undoped with lithium ions, a lithium ion doped Any of undopeable transition metal nitrides, carbon materials that can be doped / undoped with lithium ions, or mixtures thereof can be used.
  • metals or alloys that can be alloyed with lithium (or lithium ions) include silicon, silicon alloys, tin, and tin alloys. Among these, carbon materials that can be doped / undoped with lithium ions are preferable.
  • carbon materials examples include carbon black, activated carbon, graphite materials (artificial graphite, natural graphite, etc.), amorphous carbon materials, and the like.
  • the form of the carbon material may be any of a fibrous form, a spherical form, a potato form, and a flake form.
  • the amorphous carbon material examples include hard carbon, coke, mesocarbon microbeads (MCMB) fired at 1500 ° C. or less, and mesopause bitch carbon fiber (MCF).
  • the graphite material there are natural graphite and artificial graphite, and as the artificial graphite, graphitized MCMB, graphitized MCF and the like are used.
  • the thing containing a boron etc. can be used, The thing etc. which coat
  • the carbon material a graphite material coated with an amorphous carbon material or a mixture of an amorphous carbon material and a graphite material can be used.
  • carbon materials may be used alone or in combination of two or more.
  • a carbon material having a (002) plane distance d (002) of 0.340 nm or less measured by X-ray analysis is particularly preferable.
  • graphite having a true density of 1.70 g / cm 3 or more or a highly crystalline carbon material having properties close thereto is preferable.
  • Examples of the positive electrode active material constituting the positive electrode in the present invention include transition metal oxides or transition metal sulfides such as MoS 2 , TiS 2 , MnO 2 , and V 2 O 5 , LiCoO 2 , LiMnO 2 , LiMn 2 O 4 , and LiNiO. 2 , LiNi X Co (1-X) O 2 [0 ⁇ X ⁇ 1], complex oxides composed of lithium and transition metals such as LiFePO 4 , polyaniline, polythiophene, polypyrrole, polyacetylene, polyacene, dimercaptothiadiazole / polyaniline Examples thereof include conductive polymer materials such as composites.
  • a composite oxide composed of lithium and a transition metal is particularly preferable.
  • a carbon material can also be used as the positive electrode.
  • a mixture of a composite oxide of lithium and a transition metal and a carbon material can be used as the positive electrode.
  • Said positive electrode active material may be used by 1 type, and may mix and use 2 or more types. Since the positive electrode active material usually has insufficient conductivity, it is used together with a conductive auxiliary agent to constitute the positive electrode.
  • the conductive aid include carbon materials such as carbon black, amorphous whiskers, and graphite.
  • the separator in the present invention is a film that electrically insulates the positive electrode and the negative electrode and transmits lithium ions, and examples thereof include a porous film and a polymer electrolyte.
  • a microporous polymer film is preferably used as the porous film, and examples of the material include polyolefin, polyimide, polyvinylidene fluoride, and polyester.
  • porous polyolefin is preferable, and specific examples include a porous polyethylene film, a porous polypropylene film, or a multilayer film of a porous polyethylene film and a polypropylene film.
  • other resin excellent in thermal stability may be coated.
  • Examples of the polymer electrolyte include a polymer in which a lithium salt is dissolved, a polymer swollen with an electrolytic solution, and the like.
  • the nonaqueous electrolytic solution of the present invention may be used for the purpose of obtaining a polymer electrolyte by swelling a polymer.
  • the lithium secondary battery of this invention contains the said negative electrode active material, a positive electrode active material, and a separator.
  • the lithium secondary battery of the present invention can take various known shapes, and can be formed into a cylindrical shape, a coin shape, a square shape, a film shape, or any other shape. However, the basic structure of the battery is the same regardless of the shape, and the design can be changed according to the purpose.
  • An example of the lithium secondary battery of the present invention is a coin-type battery shown in FIG. In the coin-type battery shown in FIG.
  • a disc-shaped negative electrode 2 a separator 5 into which a non-aqueous electrolyte solution obtained by dissolving an electrolyte in a non-aqueous solvent, a disc-shaped positive electrode 1, stainless steel, or aluminum as necessary
  • Spacer plates 7 and 8 are stacked in this order and accommodated between positive electrode can 3 (hereinafter also referred to as “battery can”) and sealing plate 4 (hereinafter also referred to as “battery can lid”).
  • the positive electrode can 3 and the sealing plate 4 are caulked and sealed via a gasket 6.
  • non-aqueous electrolyte of the embodiment of the present invention and the lithium secondary battery using the non-aqueous electrolyte is not particularly limited, and can be used for various known uses.
  • NMR data of exemplary compound 65 1 H-NMR (270 MHz, CDCl 3 ) ⁇ (ppm): 60.5 (1.3 H, s), 5.79 (0.7 H, s), 0.99 (12 H, s), 0.98 ( 6H, s), 0.43 (8H, s), 0.40 (4H, s).
  • 1,1,1-trifluoropropan-2-one (0.99 g, 8.8 mmol) was added dropwise, and the mixture was stirred at 30 ° C. for 3 hours and at 40 ° C. for 1 hour.
  • the reaction solution was poured into an ice-cooled dilute aqueous hydrochloric acid solution, and the aqueous layer was extracted twice with ethyl acetate.
  • the combined organic layers were dried over anhydrous magnesium sulfate and concentrated under reduced pressure.
  • the obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / hexane) to give Exemplary Compound 99 (1.83 g, yield 85%).
  • Example 1 A lithium secondary battery was produced by the following procedure. ⁇ Production of negative electrode> 20 parts by mass of artificial graphite, 80 parts by mass of natural graphite, 1 part by mass of carboxymethyl cellulose, and 2 parts by mass of SBR latex were kneaded with an aqueous solvent to prepare a paste-like negative electrode mixture slurry. Next, this negative electrode mixture slurry was applied to a negative electrode current collector made of a strip-shaped copper foil having a thickness of 18 ⁇ m, dried, and then compressed by a roll press to form a sheet-shaped negative electrode comprising a negative electrode current collector and a negative electrode active material layer Got. The coating density of the negative electrode active material layer at this time was 10 mg / cm 2 , and the packing density was 1.5 g / ml.
  • this positive electrode mixture slurry is applied to a positive electrode current collector made of a strip-shaped aluminum foil having a thickness of 20 ⁇ m, dried, and then compressed by a roll press to form a sheet-like positive electrode comprising a positive electrode current collector and a positive electrode active material ( Hereinafter, also referred to as “Mn positive electrode”).
  • the coating density of the positive electrode active material layer at this time was 30 mg / cm 2 , and the packing density was 2.5 g / ml.
  • ethylene carbonate (EC), dimethyl carbonate (DMC), and methyl ethyl carbonate (EMC) were mixed at a ratio of 34:33:33 (mass ratio), respectively, to obtain a mixed solvent.
  • LiPF 6 as an electrolyte was dissolved so that the electrolyte concentration in the finally prepared nonaqueous electrolytic solution was 1 mol / liter.
  • the cyclic sulfone compound [Exemplary Compound 3] and vinylene carbonate as additives, with respect to the total amount of the nonaqueous electrolyte solution finally prepared, are 0.5% by mass, respectively.
  • a nonaqueous electrolytic solution was obtained.
  • the above-mentioned negative electrode was punched into a disk shape with a diameter of 14 mm and the above-mentioned positive electrode with a diameter of 13 mm to obtain a coin-shaped electrode.
  • a 20 ⁇ m thick microporous polyethylene film was punched into a disk shape having a diameter of 17 mm to obtain a separator.
  • the obtained coin-shaped negative electrode, separator, and coin-shaped positive electrode are stacked in this order in a stainless steel battery can (2032 size), and 20 ⁇ l of non-aqueous electrolyte is injected to be contained in the separator, the positive electrode, and the negative electrode. Soaked.
  • a coin-type lithium secondary battery (hereinafter referred to as a test battery) having a configuration of 3.2 mm shown in FIG. 1 was produced. The initial characteristics of the obtained coin-type battery (test battery) were evaluated.
  • the battery was charged at a constant voltage of 4.0 V, the battery was cooled to 0 ° C. in a thermostat, and impedance measurement was performed using a Solartron impedance measurement device (potential galvanostat SI1287 and frequency response analyzer 1255B).
  • the resistance value [ ⁇ ] at 2 Hz was defined as the initial battery resistance.
  • Table 1 The results are shown in Table 1 below.
  • Examples 2 to 15 instead of the cyclic sulfone compound [Exemplary Compound 3] used in the preparation of the non-aqueous electrolyte, the cyclic sulfone compound shown in Table 1 has a content of 0.5 mass relative to the total mass of the non-aqueous electrolyte finally prepared.
  • a coin-type lithium secondary battery was obtained in the same manner as in Example 1 except that it was added so as to be%. The obtained coin-type battery was evaluated for initial characteristics in the same manner as in Example 1.
  • Example 1 The cyclic sulfone compound [Exemplary Compound 3] used for the preparation of the non-aqueous electrolyte solution was not added, and only vinylene carbonate (VC) was used as an additive. A coin-type battery was obtained in the same manner as in Example 1 except that 5% by mass was added. The obtained coin-type battery was evaluated for initial characteristics in the same manner as in Example 1.
  • Example 16 In Example 1, a coin-type lithium secondary battery was produced and evaluated in the same manner as in Example 1 except that the Mn positive electrode was changed to the following Co positive electrode. Details are shown below.
  • ⁇ Production of negative electrode> As in Example 1, 20 parts by mass of artificial graphite, 80 parts by mass of natural graphite, 1 part by mass of carboxymethyl cellulose, and 2 parts by mass of SBR latex were kneaded with an aqueous solvent to prepare a paste-like negative electrode mixture slurry. .
  • this negative electrode mixture slurry was applied to a negative electrode current collector made of a strip-shaped copper foil having a thickness of 18 ⁇ m, dried, and then compressed by a roll press to form a sheet-shaped negative electrode comprising a negative electrode current collector and a negative electrode active material layer Got.
  • the coating density of the negative electrode active material layer at this time was 10 mg / cm 2 , and the packing density was 1.5 g / ml.
  • the coating density of the positive electrode active material layer at this time was 30 mg / cm 2 , and the packing density was 2.5 g / ml.
  • ethylene carbonate (EC), dimethyl carbonate (DMC), and methyl ethyl carbonate (EMC) were mixed at a ratio of 34:33:33 (mass ratio), respectively, to obtain a mixed solvent.
  • LiPF 6 as an electrolyte was dissolved so that the electrolyte concentration in the finally prepared nonaqueous electrolytic solution was 1 mol / liter.
  • the cyclic sulfone compound [Exemplary Compound 3] and vinylene carbonate as additives, with respect to the total amount of the nonaqueous electrolyte solution finally prepared, are 0.5% by mass, respectively.
  • a nonaqueous electrolytic solution was obtained.
  • the above-mentioned negative electrode was punched into a disk shape with a diameter of 14 mm and the above-mentioned positive electrode with a diameter of 13 mm to obtain a coin-shaped electrode. Further, a microporous polyethylene film having a thickness of 20 ⁇ m was punched into a disk shape having a diameter of 17 mm to obtain a separator.
  • the obtained coin-shaped negative electrode, separator, and coin-shaped positive electrode were laminated in this order in a stainless steel battery can (2032 size), and 20 ⁇ l of nonaqueous electrolyte was injected to impregnate the separator, the positive electrode, and the negative electrode. I let you.
  • a coin-type lithium secondary battery (hereinafter referred to as a test battery) having the configuration shown in FIG. The initial characteristics of the obtained coin-type battery (test battery) were evaluated.
  • the battery was charged at a constant voltage of 4.0 V, the battery was cooled to 0 ° C. in a thermostat, and impedance measurement was performed using a Solartron impedance measurement device (potential galvanostat SI1287 and frequency response analyzer 1255B).
  • the resistance value [ ⁇ ] at 2 Hz was defined as the initial battery resistance.
  • Table 2 The results are shown in Table 2 below.
  • Examples 17 to 30 Instead of the cyclic sulfone compound [Exemplary Compound 3] used for the preparation of the non-aqueous electrolyte, the cyclic sulfone compound shown in Table 2 is 0.5 mass relative to the total mass of the non-aqueous electrolyte finally prepared.
  • a coin-type lithium secondary battery was obtained in the same manner as in Example 16 except that it was added so as to be%. The obtained coin-type battery was evaluated for initial characteristics in the same manner as in Example 16.
  • Example 31 In the preparation of the nonaqueous electrolytic solution of Example 1, the content relative to the total mass of the nonaqueous electrolytic solution in which the cyclic sulfone compound [Exemplary Compound 2] is finally prepared instead of the cyclic sulfone compound [Exemplary Compound 3] is 0.00.
  • a non-aqueous electrolyte solution was obtained in the same manner as in Example 1 except that 5% by mass was added and that vinylene carbonate was not added.
  • a coin-type lithium secondary battery was obtained in the same manner as in Example 1 except that the obtained nonaqueous electrolytic solution was used. The obtained coin-type battery was evaluated for initial characteristics in the same manner as in Example 1.
  • Examples 32 to 48 instead of the cyclic sulfone compound [Exemplary Compound 2] used for the preparation of the non-aqueous electrolyte, the cyclic sulfone compound shown in Table 3 is 0.5 mass relative to the total mass of the non-aqueous electrolyte finally prepared.
  • a coin-type lithium secondary battery was obtained in the same manner as in Example 31 except that it was added so as to be%. The obtained coin-type battery was evaluated for initial characteristics in the same manner as in Example 31.
  • Example 5 A coin-type battery was obtained in the same manner as in Example 31 except that the cyclic sulfone compound [Exemplary Compound 2] used for the preparation of the nonaqueous electrolytic solution was not added. The obtained coin-type battery was evaluated for initial characteristics in the same manner as in Example 31.
  • Example 49 In Example 31, a coin-type lithium secondary battery was fabricated and evaluated in the same manner as in Example 31 except that the Mn positive electrode was changed to the Co positive electrode described above. That is, a non-aqueous electrolyte was obtained in the same manner as in Example 31, and a coin-type lithium secondary battery was obtained in the same manner as in Example 16 except that the obtained non-aqueous electrolyte was used. The obtained coin-type battery was evaluated for initial characteristics in the same manner as in Example 16.
  • Examples 50 to 67 instead of the cyclic sulfone compound [Exemplary Compound 2] used for the preparation of the non-aqueous electrolyte, the cyclic sulfone compound shown in Table 4 has a content of 0.5 mass relative to the total mass of the non-aqueous electrolyte finally prepared.
  • a coin-type lithium secondary battery was obtained in the same manner as in Example 49 except that the addition was performed so that the content of the lithium secondary battery would be 5%. The obtained coin-type battery was evaluated for initial characteristics in the same manner as in Example 49.
  • Example 7 A coin-type battery was obtained in the same manner as in Example 49 except that the cyclic sulfone compound [Exemplary Compound 2] used for the preparation of the nonaqueous electrolytic solution was not added. The obtained coin-type battery was evaluated for initial characteristics in the same manner as in Example 49.
  • Example 68 In the preparation of the non-aqueous electrolyte in Example 1, instead of the cyclic sulfone compound [Exemplary Compound 3] and vinylene carbonate, the cyclic sulfone compound [Exemplary Compound 6] and fluoroethylene carbonate are finally prepared.
  • a nonaqueous electrolytic solution was obtained in the same manner as in Example 1 except that the content was 1.0% by mass with respect to the total mass.
  • a coin-type lithium secondary battery was obtained in the same manner as in Example 1 except that the obtained nonaqueous electrolytic solution was used. The obtained coin-type battery was evaluated for initial characteristics in the same manner as in Example 1.
  • Example 69 A coin-type lithium secondary battery was obtained in the same manner as in Example 68 except that [Exemplary Compound 65] was added in place of the cyclic sulfone compound [Exemplary Compound 6] used in the preparation of the nonaqueous electrolytic solution. The obtained coin-type battery was evaluated for initial characteristics in the same manner as in Example 68.
  • Example 9 A coin-type lithium secondary battery was obtained in the same manner as in Example 68 except that the cyclic sulfone compound [Exemplary Compound 6] used for the preparation of the nonaqueous electrolytic solution was not added. The obtained coin-type battery was evaluated for initial characteristics in the same manner as in Example 68.
  • Example 70 In Example 68, a battery was produced and evaluated in the same manner as in Example 68 except that the Mn positive electrode was changed to the aforementioned Co positive electrode. That is, a non-aqueous electrolyte was obtained in the same manner as in Example 68, and a coin-type lithium secondary battery was obtained in the same manner as in Example 16 except that the obtained non-aqueous electrolyte was used. The obtained coin-type battery was evaluated for initial characteristics in the same manner as in Example 16.
  • Example 71 A coin-type lithium secondary battery was obtained in the same manner as in Example 70 except that [Exemplary Compound 65] was added instead of the cyclic sulfone compound [Exemplary Compound 6] used in the preparation of the non-aqueous electrolyte. The obtained coin-type battery was evaluated for initial characteristics in the same manner as in Example 70.
  • Example 11 A coin-type lithium secondary battery was obtained in the same manner as in Example 70 except that the cyclic sulfone compound [Exemplary Compound 6] used for the preparation of the nonaqueous electrolytic solution was not added. The obtained coin-type battery was evaluated for initial characteristics in the same manner as in Example 70.

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Abstract

L'invention concerne une solution d'électrolyte non aqueuse qui contient un composé sulfone cyclique ayant une structure de type 1,3-dithiéthane-1,1,3,3-tétraoxyde. Le composé sulfone cyclique est de préférence un composé représenté par la formule (I), dans laquelle R1-R4 représentent chacun un atome d'hydrogène, un atome halogène, un groupe alkyle substitué ou non substitué, ou analogue,
PCT/JP2011/060093 2010-04-26 2011-04-25 Solution d'électrolyte non aqueuse contenant un composé sulfone cyclique, et batterie secondaire au lithium WO2011136189A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP11774970.5A EP2565973B1 (fr) 2010-04-26 2011-04-25 Solution non-aqueuse d'électrolyte contenant un composé sulfone cyclique, et batterie secondaire au lithium comprenant cette dernière
CN201180020472.8A CN102870268B (zh) 2010-04-26 2011-04-25 含有环状砜化合物的非水电解液及锂二次电池
JP2012512837A JP5399556B2 (ja) 2010-04-26 2011-04-25 環状スルホン化合物を含有する非水電解液、及びリチウム二次電池
US13/643,302 US9303011B2 (en) 2010-04-26 2011-04-25 Nonaqueous electrolyte solution containing cyclic sulfone compound, and lithium secondary battery
KR1020127029926A KR101422383B1 (ko) 2010-04-26 2011-04-25 환상 설폰 화합물을 함유하는 비수전해액, 및 리튬 2차 전지

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JP2010101206 2010-04-26
JP2010-101206 2010-04-26

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WO2011136189A1 true WO2011136189A1 (fr) 2011-11-03

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US (1) US9303011B2 (fr)
EP (1) EP2565973B1 (fr)
JP (1) JP5399556B2 (fr)
KR (1) KR101422383B1 (fr)
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WO (1) WO2011136189A1 (fr)

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CN103367801A (zh) * 2012-04-09 2013-10-23 张家港市国泰华荣化工新材料有限公司 能提高锂离子电池高温性能的电解液
JP2015149234A (ja) * 2014-02-07 2015-08-20 三井化学株式会社 電池用非水電解液、及びリチウム二次電池
WO2022138452A1 (fr) * 2020-12-21 2022-06-30 株式会社Ｇｓユアサ Élément de stockage d'énergie à électrolyte non aqueux, dispositif électronique et automobile
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CN104051787B (zh) * 2014-07-02 2016-04-27 东莞市凯欣电池材料有限公司 一种非水电解液及其制备方法以及一种高电压锂离子电池
CN104051788B (zh) * 2014-07-02 2016-06-15 东莞市凯欣电池材料有限公司 非水电解液及其制备方法以及一种锂离子电池
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KR20220129390A (ko) * 2021-03-16 2022-09-23 삼성에스디아이 주식회사 신규 화합물, 이를 포함하는 첨가제, 전해질 및 리튬 이차전지
KR102395110B1 (ko) * 2021-09-24 2022-05-09 제이엘켐 주식회사 이차전지 전해질용 첨가제로 사용되는 펜타에리쓰리톨 디설페이트의 제조방법

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WO2013054511A1 (fr) * 2011-10-11 2013-04-18 株式会社Ｇｓユアサ Pile rechargeable à électrolyte non aqueux et procédé de production d'une pile rechargeable à électrolyte non aqueux
US9306238B2 (en) 2011-10-11 2016-04-05 Gs Yuasa International Ltd. Nonaqueous electrolyte secondary battery and method for producing nonaqueous electrolyte secondary battery
JPWO2013054511A1 (ja) * 2011-10-11 2015-03-30 株式会社Ｇｓユアサ 非水電解質二次電池および非水電解質二次電池の製造方法
EP2768065A4 (fr) * 2011-10-11 2015-03-18 Gs Yuasa Int Ltd Pile rechargeable à électrolyte non aqueux et procédé de production d'une pile rechargeable à électrolyte non aqueux
KR20140106495A (ko) * 2011-12-07 2014-09-03 가부시키가이샤 지에스 유아사 비수 전해질 2차 전지 및 비수 전해질 2차 전지의 제조 방법
EP2790261A1 (fr) * 2011-12-07 2014-10-15 GS Yuasa International Ltd. Batterie secondaire à électrolyte non aqueux et procédé de fabrication de batterie secondaire à électrolyte non aqueux
EP2790261A4 (fr) * 2011-12-07 2014-11-12 Gs Yuasa Int Ltd Batterie secondaire à électrolyte non aqueux et procédé de fabrication de batterie secondaire à électrolyte non aqueux
CN103843187A (zh) * 2011-12-07 2014-06-04 株式会社杰士汤浅国际 非水电解质二次电池和非水电解质二次电池的制造方法
JPWO2013084393A1 (ja) * 2011-12-07 2015-04-27 株式会社Ｇｓユアサ 非水電解質二次電池および非水電解質二次電池の製造方法
WO2013084393A1 (fr) * 2011-12-07 2013-06-13 株式会社Ｇｓユアサ Batterie secondaire à électrolyte non aqueux et procédé de fabrication de batterie secondaire à électrolyte non aqueux
US9917327B2 (en) 2011-12-07 2018-03-13 Gs Yuasa International Ltd. Nonaqueous electrolyte secondary battery and method for producing nonaqueous electrolyte secondary battery
KR102006010B1 (ko) * 2011-12-07 2019-07-31 가부시키가이샤 지에스 유아사 비수 전해질 2차 전지 및 비수 전해질 2차 전지의 제조 방법
US10749213B2 (en) 2011-12-07 2020-08-18 Gs Yuasa International Ltd. Nonaqueous electrolyte secondary battery and method for producing nonaqueous electrolyte secondary battery
CN103367801A (zh) * 2012-04-09 2013-10-23 张家港市国泰华荣化工新材料有限公司 能提高锂离子电池高温性能的电解液
JP2015149234A (ja) * 2014-02-07 2015-08-20 三井化学株式会社 電池用非水電解液、及びリチウム二次電池
WO2022138452A1 (fr) * 2020-12-21 2022-06-30 株式会社Ｇｓユアサ Élément de stockage d'énergie à électrolyte non aqueux, dispositif électronique et automobile
WO2022210803A1 (fr) * 2021-03-30 2022-10-06 セントラル硝子株式会社 Solution électrolytique non aqueuse, batterie à solution électrolytique non aqueuse et procédé de production de batterie à solution électrolytique non aqueuse

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CN102870268A (zh) 2013-01-09
US20130040209A1 (en) 2013-02-14
EP2565973B1 (fr) 2017-01-04
JPWO2011136189A1 (ja) 2013-07-18
KR20130006694A (ko) 2013-01-17
EP2565973A4 (fr) 2015-08-05
KR101422383B1 (ko) 2014-07-22
JP5399556B2 (ja) 2014-01-29
EP2565973A1 (fr) 2013-03-06
US9303011B2 (en) 2016-04-05
CN102870268B (zh) 2015-07-29

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